KR20070063134A - Method of producing hard coat and anti-reflection glaring film with conductive/magnetic particle - Google Patents

Abstract

Provided is a method of manufacturing a hard coat and anti-reflection film by substituting conductive particle for particle having conductive and magnetic features and distributing them on the transparent material film regularly so that compensate loss of time, to be more competitive at cost and productive in film production. The method of manufacturing a hard coat and anti-reflection glaring film has the steps of: containing conductive/magnetic particle(3) in the transparent resin; forming hard coat layer(2) by applying the transparent resin containing conductive/magnetic particle(3) on a transparent film material(1); localizing conductive/magnetic particle(3) of hard coat layer(2) to the transparent film material(1) in use of applied magnetic material by disposing matrix-structured applied magnetic material inside the roll in order to have regularity for all the materials; hardening the transparent resin.

Description

TECHNICAL FIELD OF PRODUCING HARD COAT AND ANTI-REFLECTION GLARING FILM WITH CONDUCTIVE / MAGNETIC PARTICLE}

1 is a cross-sectional view of the hard coat and anti-glare antireflection film produced by the manufacturing method according to the present invention.

FIG. 2 is a process flow diagram for localizing conductive / magnetic fine particles toward a transparent base film using a magnetic applicator. FIG.

3 is a process flow chart in which a film is coated by a magnetic applicator consisting of a matrix arrangement inside a roll.

4 is an inner configuration diagram of a roll in which the magnetic injector is formed in a matrix arrangement.

FIG. 5 is an arrangement diagram of conductive / magnetic fine particles coated on a transparent base film in the same arrangement by the matrix arrangement of the magnetic applicator. FIG.

<Brief description of symbols for the main parts of the drawings>

1: Transparent base film # 2: Hard coat layer

3: conductive / magnetic fine particles 4: roll

5: Magnetic Applicator X6: Matrix Structure of Magnetic Applicator

7: conductive particles coated with matrix structure

The present invention is more conductive than the conventional manufacturing method by arranging a magnetic applying body having a matrix structure inside the roll such that the distribution unevenly distributed toward the transparent base film of conductive / magnetic fine particles in the hard coat layer has regularity with respect to the entire substrate. It is characterized in that the magnetic fine particles are more regularly localized toward the transparent base film, so that the conductive / magnetic fine particles can be contained in the range that can be controlled by the magnetic applying agent.

Generally, it is indispensable to arrange | position a polarizer on both sides of the glass substrate which forms a liquid crystal panel from the image forming system, and the polarizing plate provided with the transparent protective film in one side or both sides of a polarizer is used. The transparent protective film for polarizing plates used on the viewer's side is vulnerable in terms of scratching. Therefore, the transparent protective film uses the hard coat film which formed the hard-coat layer by transparent resin layers, such as an acrylic resin and urethane acrylate resin, for the purpose of the improvement of abrasion resistance. .

In addition, static electricity is likely to be generated on the surface of a display such as a liquid crystal display, foreign matter such as dust is likely to adhere to the surface by the static electricity, and furthermore, the function itself of the display may be hindered by the static electricity. Therefore, the said hard coat film used for a polarizing plate etc. provides the transparent conductive layer between a transparent protective film and a hard coat layer in order to provide antistatic property, and prevents the damage by static electricity. The said transparent conductive layer is formed of the transparent conductive layer forming material which disperse | distributed electroconductive fine particles in transparent resin.

However, there is a problem in that adhesion to the hard coat layer formed on the transparent conductive layer is insufficient when the transparent conductive layer contains a sufficient amount of the conductive fine particles so as to eliminate the damage caused by static electricity. Moreover, in order to improve the said adhesiveness, although the method of forming a hard-coat layer with a half-cure (half cure) can also be considered, there exists a possibility that a scratch etc. may enter in a transparent conductive layer, and there exists a problem which is difficult to employ | adopt.

In addition, the conductive fine particles contained in the transparent conductive layer can localize the conductive fine particles to the transparent base film side by using a specific gravity difference with the transparent resin as in Japanese Patent (JP 2002-19206). However, such a method causes a time loss of waiting for the conductive fine particles to settle due to the specific gravity difference, which has been a factor in weakening the productivity and price competitiveness of the film. In addition, since the regularity on the substrate of the conductive fine particles can also be regarded as an important object of consideration, this situation needs to be considered.

The present invention has been made to solve the above problems, and the fine particles having both the conductive fine particles and the conductive fine particles, rather than a method of ubiquitous toward the transparent base film by using the difference in specific gravity of the transparent resin and the conductive fine particles constituting the hard coat layer. And a method of ubiquitous in a regular form on the transparent substrate film was devised. In this way, the conductive fine particles of the hard coat layer using the specific specific gravity difference are not only overcome the time loss, which is a disadvantage of the ubiquitous method, but also the conductive fine particles are arranged on a transparent substrate film in a more regular form, thereby producing the film. It is an object of the present invention to design the distribution and arrangement of the conductive fine particles on the transparent substrate film in a more regular form while increasing productivity and cost competitiveness.

The above and other objects and advantages of the present invention will become more apparent from the following description of the preferred embodiments with reference to the accompanying drawings.

Method for producing a hard coat and anti-glare antireflection film according to the present invention for achieving the above object is a method for producing a hard coat and anti-glare anti-reflection film having a hard coat layer made of a transparent resin on a transparent base film The method comprising the steps of: containing conductive / magnetic fine particles in the transparent resin; Applying a transparent resin containing the conductive / magnetic fine particles on a transparent base film to form a hard coat layer; The conductive / magnetic fine particles of the hard coat layer are localized toward the transparent base film by using a magnetic applicator, and the distribution of the conductive / magnetic fine particles toward the transparent base film in the hard coat layer has regularity with respect to the entire substrate. And arranging the magnetic application body having a matrix structure inside the roll so as to have a localization, and hardening the transparent resin.

Preferably, the conductive / magnetic fine particles of the hard coat layer are unevenly distributed in a concentration distribution in the thickness direction, and the concentration of the conductive / magnetic fine particles is higher toward the transparent base film. More preferably, the step of ubiquitous the conductive / magnetic fine particles toward the transparent substrate film using the magnetic applicator may include at least 70% of the conductive / magnetic fine particles contained in the transparent substrate relative to the total thickness of the hard coat layer. It is ubiquitous in thickness of 0.7 or less from a film, It is characterized by the above-mentioned.

In addition, it is characterized in that the conductive / magnetic fine particles are ubiquitous in a regular and constant distribution without agglomeration due to the influence of the magnetic application body having the matrix structure inside the roll.

Hereinafter, the present invention will be described in detail with reference to embodiments and drawings of the present invention. These examples are only presented by way of example only to more specifically describe the present invention, it will be apparent to those skilled in the art that the scope of the present invention is not limited by these examples. .

In the production method according to the present invention, in the hard coat having the hard coat layer 2 formed of the transparent resin on the transparent base film 1 and the anti-glare antireflection film, the conductive / magnetic properties are included in the hard coat layer. It is related with the manufacturing method of the hard-coat and anti-glare film characterized by the microparticles | fine-particles 3 having a density distribution in the thickness direction, and having the density of electroconductive / magnetic microparticles increasing to the transparent base film 1 side. . In particular, the magnetic application body of the matrix structure 6 is arrange | positioned inside the roll 5 so that the distribution localized to the base material of electroconductive / magnetic fine particle may be regular with respect to the whole base material.

In this invention, electroconductive / magnetic microparticles | fine-particles 3 are unevenly distributed on the transparent base film 1 side in the hard-coat layer 2, and in the hard-coat layer 2, the transparent base film 1 side is an external appearance. The transparent conductive layer (henceforth an external appearance transparent conductive layer) is formed. As a result, in the hard coat layer 2 on the transparent base film 1 side, an electroconductive characteristic is ensured by an externally transparent conductive layer, and scratch resistance is ensured in the hard coat layer on the opposite side. Since the conductive properties and the scratch resistance can be formed at a time by a single hard coat layer, there is no problem of poor adhesion. In addition, if the conductive / magnetic fine particles 3 are uniformly distributed in the hard coat layer 2, the conductivity of the conductive / magnetic fine particles 3 decreases, so that the conductivity becomes difficult to develop.

The degree of localization of the electroconductive / magnetic fine particles 3 in the hard coat layer 2 can be performed by cross-sectional observation by TEM or the like. The degree of ubiquitous is, for example, the ratio L2 of the thickness L2 of the hard coat layer 2 on the transparent base film 1 side to the thickness L1 of the hard coat layer 2, as shown in FIG. 1. / L1) refers to a case in which 40% or more and 70% or more of the conductive / magnetic fine particles 3 in the hard coat layer 2 are included in the range of the thickness L2 of 0.7 or less. The ratio L2 / L1 of the thickness is more preferably 0.5 or less.

With respect to the hard coat and the anti-glare antireflection film, the conductive / magnetic fine particles 3 are preferable to be localized on the transparent base film 1 side. To this end, after preparing a solution in which the fine particles 3 having both conductivity and magnetism are dispersed in the resin, the fine particles can be localized to the transparent base film 1 side using the magnetic applying body 5 as shown in FIG. 2. . At this time, an appropriate magnetic force must be applied so that the conductive / magnetic fine particles 3 are not excessively localized to any part of the transparent base film 1 due to the excessive magnetic force of the magnetic application body 5. In addition, the conductive / magnetic fine particles 3 may be uniformly localized on the transparent base film 1 side by the magnetic force of the magnetic applying body 3 so that the viscosity of the resin containing the conductive / magnetic fine particles 3 is not too large.

Here, the magnetic application body 5 is in contact with the transparent base film 1 is the same as the shape of a general roll, but the magnetic application body 6 inside the roll is characterized in that the matrix structure. The matrix of the magnetic applicator 6 is formed such that the conductive / magnetic microparticles 3 precoated by the microgravure 4 by the magnetic applicator 6 having the matrix structure are localized toward the transparent base film 1. By forming in the same manner as the structure can be arranged 7 on the transparent base film (1) more accurately and regularly than the conventional method for coating the conductive particles. The above-described technique enables the coating of the conductive / magnetic particles on the transparent base film 1 in an accurate and regularly arranged form, thereby eliminating the problem of aggregation of fine particles in the existing coating method and arrangement. Can also be applied to the electromagnetic shielding function.

It is preferable that the hard-coat (2) layer is formed of 2 or more types of transparent resin about the said hard coat and anti-glare antireflection film. In the formation of the hard coat layer 2, in particular, by using two or more kinds of transparent resins having different specific gravity, the external appearance transparent conductive layer can be formed more easily.

Moreover, this invention relates to the hard coat film characterized by the reflection prevention layer being formed on the hard coat layer 2 of the said hard coat and anti-glare antireflection film. The hard coat and anti-glare antireflection film of the present invention can be used as an antireflection hard coat film having a low reflectance by forming an antireflection layer.

Moreover, this invention relates to the optical element characterized by the said hard-coat and anti-glare antireflection film provided in the single side | surface or both surfaces of an optical element. Moreover, this invention relates to the image display apparatus which mounted the said hard coat film or optical element. Optical elements, such as a polarizing plate using the hard-coat and anti-glare antireflection film of this invention, are excellent in abrasion resistance and electrically conductive characteristics, and there is no problem also in inadequate adhesion. Moreover, it is excellent also in an optical characteristic. Moreover, an optical element can be used for various uses, and image display apparatuses, such as a liquid crystal display device in which this is mounted, has good display quality.

As the said transparent base film 1, it is preferable that it is excellent in transparency, mechanical strength, thermal stability, moisture covering property, isotropy, etc. For example, cellulose-based polymers such as polyester-based polymers such as polyethylene terephthalate and polyethylene naphthalate, triacetyl cellulose, And films made of transparent polymers such as polycarbonate-based polymers, acrylic polymers such as poly methyl methacrylate, and the like. . Also, styrene-based polymers such as polystyrene, acrylonitrile, and styrene copolymers, polyolefins having a polyethylene, polypropylene, norbornene structure Olefin-based polymers such as ethylene and propylene copolymers, vinyl chloride-based polymers, and amide-based compounds such as nylon and aromatic polyamides. Also mentioned are films made from transparent polymers such as polymers. In addition, amide-based polymers, sulfone-based polymers, polyether sulfone-based polymers, polyether ether ketone-based polymers, and polyphenylene sulfides ) -Based polymer, vinyl alcohol-based polymer, vinylidene chloride-based polymer, vinyl butyral-based polymer, allylate-based polymer, Also mentioned are films made from transparent polymers such as polyoxymethylene-based polymers, epoxy-based polymers, or blends of such polymers. A transparent protective film is often preferable to the extent that optical properties such as phase difference are less anisotropic.

Although the thickness of the said transparent base film 1 can be suitably determined, it is about 10-300 micrometers generally from a viewpoint of workability, thinness, etc., such as strength and handleability. 20-300 micrometers is especially preferable, and 30-300 micrometers is more preferable. The refractive index of the transparent base film 1 is about 1.43-1.60, and about 1.45-1.50 is preferable.

The transparent resin for forming the hard coat layer 2 is not particularly limited as long as it is excellent in hard coat properties (having a hardness of H or higher by the pencil hardness test of JISK5400), has sufficient strength, and is excellent in light transmittance. For example, thermosetting resin, thermoplastic resin, ultraviolet curable resin, electron beam curable resin, two-component mixed resin, etc. are mentioned. Among these, an ultraviolet curable resin which can form a light diffusion layer efficiently in a simple processing operation in a curing treatment by ultraviolet irradiation is very suitable. Examples of the ultraviolet curable resin include polyester based, acryl based, urethane based, amide based, silicone based, epoxy based, and the like. Monomers, oligomers, polymers and the like. UV-curable resins that are preferably used include, for example, those having an ultraviolet polymerizable functional group, and among them, an acrylic monomer or oligomer having two or more, particularly three to six, functional groups. The thing containing the component of the is mentioned. Moreover, an ultraviolet polymerization initiator is mix | blended with ultraviolet curable resin.

In addition, examples of the transparent resin for forming the hard coat layer 2 include sol-gel-based materials using metal alkoxides such as alkoxy silane alkoxy titan. Can be. Among these, alkoxy silane is preferable. By these, a polysiloxane structure is formed. Specific examples of alkoxy silanes include tetra methoxy silane, tetra ethoxy silane, tetra propoxy silane and tetra iso propoxy silane. tetra alkoxy silanes such as silane, tetra butoxy silane, methyl trimethoxy silane, methyl tripropoxy silane, methyl tributoxy silane butoxy silane, ethyl trimethoxy silane, n-propyl trimethoxy silane, isopropyl trimethoxy silane, vinyl trimethoxy silane, 3-gly Trialkoxy silanes such as propyl trimethoxysilane, phenyl trimethoxy silane, dimethyl dimethoxy silane, dimethyl diethoxy silane oxy silane), diethyl dimethoxy silane, diethyl diethoxy silane, and the like. Such alkoxy silane can be used as the partial condensate and the like. Among these, tetra alkoxy silanes or such partial condensates are preferred. Tetra methoxy silane, tetra ethoxy silane or such partial condensates are preferred.

Moreover, when using 2 or more types of transparent resins, as a transparent resin which forms an externally transparent conductive layer, metal alkoxides, such as an alkoxy silane, are selected, and it is transparent resin which forms another hard-coat layer. It is preferable to select an ultraviolet curable resin such as acryl or acryl urethane.

Examples of the conductive / magnetic fine particles 3 include ultrafine particles such as Ferrite. It is preferable that the average particle diameter of electroconductive / magnetic ultrafine particle is about 0.1 micrometer or less normally. The amount of the conductive / magnetic fine particles 3 to be used is not particularly limited as long as the externally transparent conductive layer is in an amount capable of exhibiting antistatic properties. Usually, it is preferable to mix | blend 5-95 weight part and 10-90 weight part with respect to 100 weight part of electrically transparent resins (solid content).

The formation method of the said hard-coat layer 2 will not be restrict | limited especially if the electroconductive / magnetic microparticles | fine-particles 3 form the thing of the state unevenly distributed on the transparent base film 1 side. For example, a transparent resin solution containing conductive / magnetic fine particles 3 is applied to the transparent base film 1, and the conductive / magnetic fine particles 3 are formed using the magnetic application body 5 as shown in FIG. After uneven distribution on the transparent substrate film 1 side, a method of curing the transparent resin to form the hard coat layer 2 can be employed. When the electroconductive / magnetic fine particles 3 are unevenly distributed, the density of the electroconductive fine particles 3 becomes high, and as a result, electroconductivity develops and surface resistance value becomes small.

In the structure of the magnetic applicator 5 of the matrix structure, the width of the line is preferably 5 to 25 µm, the width of the line is about 200 to 400 µm, particularly the width of the line is 7 to 14 µm and the width of the line is 250 to 350 µm. In addition, it is preferable that the angle of the line | wire which crosses a line | wire is 900.

In addition, the coating of the transparent resin solution is a bar coater such as a wire bar, a microgravure coater, a die coater, a casting, a spin coat. And coating in a suitable manner. As the solvent for dissolving the transparent resin, toluene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl iso butyl ketone, and isopropyl alcohol common solvents such as alcohol) and ethyl alcohol. The sedimentation of the electroconductive / magnetic fine particles 3 can be confirmed by TEM observation.

On the other hand, the thickness of the hard coat layer 2 is not particularly limited, but is preferably about 1 to 10 µm, particularly preferably 3 to 5 µm. It is preferable to adjust the refractive index of the hard-coat layer 2 higher than the refractive index of the transparent base film 1 from a viewpoint of an optical characteristic. In addition, to the hard coat layer 2, ultrafine particles of a high refractive index metal and a metal oxide can be added to adjust the high refractive index. Examples of the high refractive index ultrafine particles include ultrafine particles of metal oxides such as TiO ₂ , SnO ₂ , ZnO ₂ , ZrO ₂ , and aluminum oxide. It is preferable that the average particle diameter of such ultrafine particles is about 0.1 micrometer or less normally. The ultra-high refractive index ultrafine particles can be uniformly dispersed in most of the hard coat layer 2. It is preferable to adjust the refractive index of the hard-coat layer 2 higher than an externally transparent conductive layer as an improvement of an antireflection function. It is preferable that the refractive index of an externally transparent conductive layer is 1.50-1.65, 1.57-1.63, and other hard-coat layer refractive index is 1.55-1.85, and 1.65-1.75. The surface of the hard coat layer 2 has a fine concavo-convex structure and can provide anti-glare property. By making the surface of the hard coat layer into an uneven shape, anti-glare property by light diffusion can be imparted. The provision of light diffusivity is also desirable to reduce the reflectance.

The method for forming the fine concavo-convex structure on the surface is not particularly limited, and an appropriate method can be adopted. For example, the surface of the transparent base film 1 used for the formation of the hard coat layer 2 may be prepared in advance by sand blast, emboss roll, chemical etching, or the like. The method of forming the surface of the material itself which forms the hard-coat layer 2 in a fine concavo-convex structure by the method of roughening by the method and giving a fine concavo-convex structure to the film surface, etc. are mentioned. Moreover, the method of coating and adding another method hard coat layer 2 on the hard-coat layer 2, and giving a fine concavo-convex structure to the surface of this resin film layer by the transfer method with a metal mold | die etc. are mentioned. Moreover, the method of disperse | distributing an inorganic or organic spherical or amorphous filler to the hard-coat layer 2, and giving a fine concavo-convex structure, etc. are mentioned. The formation method of these fine uneven | corrugated structures may be formed as a layer which combined 2 or more types of methods, and combined the surface of the fine uneven structure of a different state.

As a method of forming the hard coat layer 2 on the surface of the fine uneven structure, a method of providing the hard coat layer 2 containing dispersion of inorganic or organic spherical or irregular fillers from the viewpoint of formability or the like is provided. desirable. As the inorganic or organic spherical or amorphous filler, for example, various polymers such as PMMA (poly methyl methacrylate), polyurethane, polystyrene, melamine resin ( inorganic particles such as crosslinked or uncrosslinked organic fine particles made of polymer, glass, silica, alumina, calcium oxide, titanium dioxide, zirconium oxide, zinc oxide, And conductive inorganic particles such as tin oxide, indium oxide, cadmium oxide, antimony oxide, or a composite thereof. It is preferable that the average particle diameter of the said filler is 0.5-10 micrometers, Furthermore, 1-4 micrometers. When forming a fine uneven structure by microparticles | fine-particles, it is preferable that the usage-amount of microparticles | fine-particles shall be about 1-30 weight part with respect to 100 weight part of resin.

In addition, additives, such as a leveling agent and an antistatic agent, can be contained in formation of the hard-coat layer (anti-glare layer) 2. In the formation of the hard coat layer (anti-glare layer) 2, by containing a cheek sotropy agent (silica, mica, etc. of 0.1 µm or less), fine concavo-convex structure is easily formed by the protruding particles on the anti-glare layer surface. Can be formed.

Although the formation method of an antireflection layer is not restrict | limited, The wet coating method using the low refractive index material of refractive index lower than the refractive index of the hard-coat layer 2 is a simple and easy method compared with the vacuum vapor deposition method etc., and is preferable. Examples of the material for forming the antireflection layer include resin materials such as an ultraviolet curable acrylic resin, hybrid materials in which inorganic fine particles such as colloidal silica are dispersed in the resin, and tetraethoxy silane (tetra). sol-gel-based materials using metal alkoxides such as ethoxy silane. In addition, a fluorine group containing compound is used for each material in order to provide the antifouling property of the surface. From the standpoint of scratch resistance, the low refractive index layer material having a high inorganic component content tends to be excellent, and a sol-gel material is particularly preferable. The sol-gel-based material can be partially condensed and used.

According to the present invention, the conductive fine particles are replaced by the fine particles 3 having both conductivity and magnetism, rather than a method of ubiquitous toward the transparent base film by using the difference in specific gravity between the transparent resin constituting the hard coat layer 2 and the conductive fine particles. In addition, as a method of ubiquitous the conductive / magnetic fine particles toward the transparent base film 1 using the magnetic material (5), a time loss which is a disadvantage of the ubiquitous method of transferring the conductive fine particles of the hard coat layer using the conventional specific gravity difference toward the transparent base film is avoided. As well as overcoming, by arranging the magnetic applicator inside the roll in contact with the substrate in a matrix structure, the substrate-side localization of the conductive / magnetic fine particles can be regularly and accurately in the form of a matrix such as the magnetic applicator. Agglomeration of fine particles does not occur and has the effect of being ubiquitous in a regular and constant distribution.

Claims (3)

In the method of manufacturing the hard-coat and anti-glare antireflection film which have a hard-coat layer which consists of transparent resin on a transparent base film, Containing conductive / magnetic fine particles in the transparent resin; Applying a transparent resin containing the conductive / magnetic fine particles on a transparent base film to form a hard coat layer; The conductive / magnetic fine particles of the hard coat layer are localized toward the transparent base film by using a magnetic applicator, and the distribution of the conductive / magnetic fine particles toward the transparent base film in the hard coat layer has regularity with respect to the entire substrate. Arranging and distributing a magnetic application body having a matrix structure inside the roll to have it; Curing the transparent resin, characterized in that the hard coat and anti-glare anti-reflection film production method. The method of claim 1, The conductive / magnetic fine particles of the hard coat layer are unevenly distributed in a concentration distribution in the thickness direction, and the concentration of the conductive / magnetic fine particles is gradually increasing toward the transparent base film. Manufacturing method. The method according to claim 1 or 2, The step of ubiquitous the conductive / magnetic fine particles toward the transparent base film using the magnetic applying body is performed in which 70% or more of the conductive / magnetic fine particles contained is 0.7 or less from the transparent base film relative to the total thickness of the hard coat layer. It is unevenly distributed in the thickness of the manufacturing method of the hard coat film characterized by the above-mentioned.

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